EPR-SPECTROSCOPIC INVESTIGATION OF THE SELF-EXCHANGE ELECTRON-TRANSFER RATE CONSTANTS AND REORGANIZATION ENERGIES FOR SOME ELECTROCHEMICALLY GENERATED RADICALS

The electron transfer rate constants for self-exchange reactions betwe en 4-methoxycarbonyl-1-methylpyridinium cation (1(+)) and its radical( 1(.)), azulene (2) and azulene radical anion (2(-.)) and 2,5-di-tert-b utyl-1,4-dimethoxybenzene (3) and its radical cation (3(+.)) have been investigated by EPR line-broadening measurements in DMF or acetonitri le. The aromatic radicals were generated electrochemically in an impro ved flow cell. The rate constants were determined in the slow exchange region, and the self-exchange reorganization energies were calculated .